UNIVERSITY  OF  CALIFORNIA  PUBLICATIONS 

IN 

AGRICULTURAL   SCIENCES 

Vol.  4,  No.  10,  pp.  245-337,  35  text  figures  March  22,  1922 


EQUILIBRIUM  STUDIES  WITH  CERTAIN  ACIDS 

AND  MINERALS  AND  THEIR  PROBABLE 

RELATION  TO  THE  DECOMPOSITION 

OF  MINERALS  BY  BACTERIA 

BY 

DOUGLAS  WRIGHT,  Jr. 


CONTENTS 

PAGE 

Introduction 245 

Object  of  investigation 249 

Method  of  attack  and  theory 250 

Experimental  methods 255 

Data 257 

Summary 263 


INTRODUCTION 

The  importance  of  the  bacterial  population  to  the  soil  is  well  recog- 
nized. The  role  of  micro-organisms  in  the  processes  of  ammonification, 
of  nitrification,  and  of  nitrogen  fixation  has  been  the  subject  of  so  much 
investigation,  and  has  been  reviewed  so  often  in  the  literature  that  it  is 
generally  accepted  as  fact.  The  influence  of  bacterial  life,  or  of  the  end- 
products  resulting  therefrom,  causing  as  it  does  the  solution  of  necessary 
plant  nutrients  from  the  mineral  particles  within  the  soil,  has  been  the 
object  of  much  speculation,  some  of  which  has  been  substantiated  by 
experiment.  Aside  from  this  effect  of  bacteria  upon  the  mineral  particles 
within  the  soil,  there  is  some  reason  for  believing  that  rocks  may  undergo 
disintegration  and  degradation  into  soil  through  the  action  of  bacteria. 
This  subject  has  been  discussed  and  investigated  at  some  length  by 
various  writers,  whose  work  will  be  mentioned  later. 

The  formation  of  the  mineral  portion  of  the  soil  is  due  to  the  opera- 
tion upon  the  rock  mass  of  three  general  factors,  namely,  changes  in 


246  University  of  California  Publications  in  Agricultural  Sciences        [Vol.4 

physical  environment,  chemical  action,  and  biological  activity.  The  first 
of  these  exerts  so  apparent  an  influence  upon  rocks  that  it  has  long  been 
recognized  and  subjected  to  careful  investigation  by  geologists.  As 
applied  to  soils,  these  effects  belong  in  the  realm  of  the  soil  physicist  and 
therefore  will  not  be  considered  in  this  paper. 

The  chemical  agencies  chiefly  instrumental  in  breaking  down  and 
dissolving  mineral  material  are  water,  solutions  of  varying  amounts  of 
NH3  and  C02,  various  salts,  organic  acids,  and  organic  compounds. 
The  effect  of  solutions,  especially  of  neutral  salts,  has  been  the  subject 
of  extensive  investigation.  This  work  will  be  reviewed  later  in  the 
section  of  this  paper  dealing  with  method  of  attack  and  theory. 

Certain  biological  activities  are  generally  acknowledged  to  be  op- 
erative in  breaking  down  the  rock  mass  and  preparing  it  for  use  as  a 
suitable  medium  for  the  growth  of  plants.  Some  of  these  are  mechanical, 
such  as  the  manifest  action  of  roots  in  prying  apart  portions  of  rock. 
Other  effects  on  rocks  are  far  less  easily  discernible,  due  to  the  slight 
action  of  a  vast  population  of  microscopic  flora  found  upon  rock  in  all 
stages  of  its  decomposition.  The  growth  of  algae,  both  alone  and  in 
their  symbiotic  relationships  with  the  lichens,  may  aid,  through  the 
effect  of  respiration  products,  in  the  solution  of  minerals.  It  is  likely, 
however,  that  the  more  important  office  of  these  simple  green  plants  is 
to  serve  directly  or  indirectly  as  a  source  of  energy  for  the  growth  of  the 
still  smaller  organisms — the  bacteria — in  situations  where  the  supply  of 
organic  materials  is  limited. 

A  statement  concerning  the  effect  of  bacteria  in  rock  decomposition 
was  made  by  Muntz1  as  early  as  the  year  1890.  He  found  bacteria  "in 
the  denuded  rocks  of  the  Alps,  the  Pyrenees,  the  Auvergne,  and  the 
Vosges  comprising  the  most  varied  mineralogical  types:  granites,  por- 
phyries, gneiss,  mica  schist,  volcanic  rocks,  limestones,  and  sandstones, 
.  .  .  Often  the  action  is  not  confined  to  the  surface,  but  extends  into 
the  depth  of  the  rock  mass.  This  is  the  case  with  the  so-called  rotten 
rocks  of  which  the  particles  become  disengaged  and  separate  as  is  often 
seen  in  limestones,  schists,  and  granites.  ...  In  decomposed  rocks 
I  have  always  verified  the  presence  of  nitrifying  organisms." 

Branner2  takes  issue  with  Muntz's  assumptions,  citing  the"  need  of 
bacteria  for  a  large  supply  of  oxygen  and  nitrogen,  and  their  sapro- 
phytic  habit  as  prohibitive  of  their  growth  to  any  extent  upon  or  in 
rocks.  J  bid  Branner's  statements  been  made  some  years  later,  they 
undoubtedly  would  have  been  modified  by  recent  information  con- 
cerning the  nitrogen  compounds  of  the  fundamental  rocks.  The  in- 
vest igations  of  IIa.ll  and  Miller3  show  that  part  of  the  nitrogen  in  certain 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  247 

clay  soils  may  have  been  derived  from  the  nitrogen  compounds  in  the 
rocks  from  which  those  soils  were  formed. 

Merrill4  mentions  bacteria  as  possible  agencies  in  the  decomposition 
of  rocks. 

Renault5  found  bacteria  present  in  coal,  and  postulates  their  action 
in  coal  beds  as  that  of  the  transformation  of  carbonaceous  material 
into  methane  and  hydrogen. 

Holland6  suggests  that  the  phenomenon  of  laterization  may  be  due 
to  the  action  of  bacteria,  possibly  to  some  specific  organism  allied  to  the 
sulfur  and  iron  bacteria,  and  gives  certain  observations  which  lead  to 
this  belief. 

Lacroix7  makes  the  following  statement:  "The  bare  rocky  islet  of 
Cabras,  near  San  Thome  in  the  Gulf  of  Guinea,  is  covered  with  a  mantle 
of  slightly  ferruginous  aluminum  phosphate  which  is  sometimes  several 
centimeters  thick.  This  has  originated  from  the  interaction  of  some  of 
the  products  of  bird  guano  and  the  underlying  rock,  aided,  doubtless, 
by  microbes." 

All  the  conclusions  in  the  literature  mentioned  thus  far  are  of  a 
conjectural  character  and  are  the  result  of  observation  only,  no  con- 
trolled or  investigational  work  having  been  presented  in  support  of  the 
opinions  offered.  The  most  important  systematic  investigation  of  the 
action  of  bacteria  on  rocks  was  undertaken  by  K.  Bassalik8,  and  is 
reported  by  him  in  two  papers,  The  Decomposition  of  Silicates  by  Soil 
Bacteria,  and  The  Decomposition  of  Silicates  by  Soil  Bacteria  and  Yeasts. 

The  first  of  these  papers  is  more  or  less  preliminary,  the  author 
drawing  the  conclusion  that  bacteria  are  able  to  derive  their  necessary 
mineral  nutrients  from  the  feldspars,  and  that  appreciable  quantities  of 
unweathered  orthoclase  are  dissolved  by  bacteria,  probably  by  means 
of  C02  produced  by  the  latter. 

The  second  paper  reports  an  elaborate  study  of  the  effect  of  the 
growth  of  several  organisms  upon  various  minerals.  B.  extorquens, 
several  of  the  nitrifying  organisms,  butyric  acid  bacteria,  and  yeasts 
were  tried  upon  twelve  widely  varying  silicates  and  upon  apatite.  A 
partial  summary  of  Bassalik's  results  is  given  here: 

1.  Bacteria  are  able  by  means  of  their  products  of  respiration  to  cause  a 
significant  solubility  of  pulverized  silicates. 

2.  Those  which  produce  organic  acids,  as  Clostridium  Pasteurianum,  influence 
more  strongly  the  solubility  of  the  silicates. 

3.  In  the  action  of  micro-organisms  upon  rocks,  the  intensity  of  contact  of 
the  organism  and  the  mineral  to  be  dissolved  is  of  greater  importance  than  the 
various  agents  of  solubility. 

4.  Thus,  B.  extorquens,  which  produces  only  C02,  has  the  strongest  solvent 
effect  through  its  close  and  firm  envelope  of  the  mineral  particles. 


248  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 

5.  Yeasts,  which  produce  much  more  C02  in  cultures  than  B.  extorquens  , 
cause  a  smaller  solubility  because  of  the  absence  of  the  close  contact  with  the  mineral 
particles. 

6.  The  nitrite  bacteria  are  also  able  to  effect  a  significant  solubility  of  silicates 
as  the  result  of  their  physiological  property  of  oxidizing  NH3,  but  they  affect  those 
minerals  rich  in  alkaline  earths  much  more  than  those  rich  in  silicates. 

7.  The  significant  solubility  of  apatite  seems  to  be  a  property  only  of  those 
bacteria  which  produce  organic  acids,  for  this  mineral  is  dissolved  only  in  moderate 
degree  by  those  organisms  which  produce  C02. 

8.  In  the  filtrates  of  the  bacterial  cultures,  especially  with  B.  extorquens,  can 
be  recovered  all  the  chemical  constituents  present  in  the  minerals  experimented 
with.  Those  most  easily  going  into  solution  are  the  alkalis,  then  the  alkaline  earths 
and  iron,  silicic  acid  much  less,  and  clay  the  least. 

This  summary  presents  some  interesting  conclusions;  and  a  close 
review  of  the  paper  shows  that  they  are  the  result  of  careful  work. 
Bassalik,  however,  does  not  get  at  the  fundamental  causes  of  the 
differences  in  the  effects  of  organisms.  This  investigator  refers,  in 
conclusions  3,  4,  and  5,  to  the  closeness  of  contact  of  organisms  to  the 
mineral  as  an  important  factor  in  determining  the  magnitude  of  the 
action  of  B.  extorquens;  but  he  does  not  offer  plausible  proof  of  this 
assumption,  and  it  would  seem  that  his  conclusion  concerning  this 
point  may  be  erroneous.  If  we  have  in  solution  H2C03  from  the  pro- 
duction of  CO2  by  B.  extorquens,  the  concentration  of  the  acid  should 
depend  upon  the  partial  pressure  of  the  C02  above  the  liquid  and  the 
rate  of  C02  production  by  the  organism.  The  same  should  be  true 
with  the  yeast,  and  as  the  yeast,  according  to  Bassalik's  own  state- 
ment, produces  C02  more  rapidly  than  does  B.  extorquens,  and  if, 
as  he  also  states,  the  solubility  is  effected  by  the  concentration  of  C02, 
the  yeast  should  effect  the  greater  solution  of  the  mineral.  This  should 
be  true,  both  in  the  solution  culture  and  in  the  solution  film  surrounding 
the  mineral  particles,  where  the  organisms  are  grown  upon  the  moist 
mineral.  Thus  it  would  seem  that  any  greater  effect  of  B.  extorquens 
should  be  attributed  to  some  specific  action  on  the  mineral,  such  as 
oxidation,  hydration,  etc.,  rather  than  to  C02.  Furthermore,  the  bac- 
terial envelope,  which  is  referred  to  as  enclosing  the  mineral  particles, 
may  consist  of  a  gelatinous  coating  produced  from  the  mineral  particle 
itself,  rather  than  of  an  aggregate  of  bacteria  (this  coating  being  greater 
where  the  action  upon  the  mineral  is  greater). 

In  1915  T.  Kawamura9  described  an  organism  found  in  some 
volcanic  material  upon  one  of  the  mountains  of  Japan,  at  an  altitude  of 
6,600  feet.  This  organism  is  of  special  interest  as  one  which  has  a 
specific  ad  ion  upon  a  silicate  material.  It  forms  a  zoogloeic  mass,  the 
ash  of  which  contains  an  unusually  large  amount  of  silica,  8.873  per 
cent.  Kawamura  proposed  the  name  Volcanothrix  silicophila  for  the 
organism. 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  249 

A  comprehensive  discussion  of  the  action  of  bacteria  upon  minerals 
would  not  be  complete  without  some  reference  to  the  action  of  certain 
organisms  upon  the  iron,  sulfur,  and  phosphorus  compounds  found  in 
rocks  and  soils.  However,  since  it  is  the  purpose  of  this  paper  to  deal 
with  an  entirely  different  phase  of  the  subject,  a  brief  reference  to  the 
bacterial  processes  affecting  these  compounds  will  suffice. 

Lipman  and  McLean10  studied  the  effect  of  the  oxidation  of  sulfur 
upon  rock  phosphate  and  found  appreciable  amounts  of  the  phosphate 
dissolved  through  the  action  of  the  resulting  acid. 

Stoklasa11  found  marked  solubility  of  bone  meal  through  the  action 
of  soil  bacteria  and  attributed  it  to  the  action  of  enzymes  upon  the 
bone  meal. 

Koch  and  Kroeber12  and  later  Kroeber13  determined  the  solubility 
of  different  forms  of  phosphate  in  the  acids  produced  by  the  growth  of 
soil  and  sewage  organisms  upon  dextrose.  Kroeber  concluded  that  the 
acids  produced  by  bacteria  and  yeasts  in  the  soil  may  be  of  great  im- 
portance in  rendering  phosphate  soluble.  In  cultures  where  CaC03  was 
present  little  or  no  phosphate  was  made  soluble. 

Sackett,  Patten,  and  Brown14  in  a  somewhat  similar  work  found 
that  there  was  a  decided  solution  of  the  insoluble  phosphate  when 
bacterial  growth  was  accompanied  by  acid  formation.  They  believed 
that  acid  is  not  the  sole  solvent. 

Hopkins  and  Whiting15  discuss  the  effect  upon  rock  phosphate  of  the 
nitrous  acid  produced  through  the  oxidation  of  NH3  by  Nitrosomonas. 


OBJECT  OF  INVESTIGATION 

Bacteria  may  effect  the  solution  and  disintegration  of  minerals  in 
at  least  two  ways: 

1.  Through  the  oxidation  or  reduction  of  one  or  more  of  the  con- 
stituents of  the  mineral  by  specific  organisms. 

2.  By  the  action  of  some  end-product  of  bacterial  activity:  i.  e., 
H  ion  resulting  from  acid  produced,  or  OH  ion  from  the  production  of 
NH3. 

In  the  present  investigation  some  of  the  fundamental  considerations 
in  connection  with  the  second  phase  of  the  subject  were  studied,  the 
work  being  limited  to  the  effect  of  acid  end-products.  In  none  of  the 
work  reviewed  in  the  foregoing  section  have  attempts  been  made  to 
obtain  results  which  may  be  used  to  determine  whether  the  action  of 
bacteria  upon  minerals  may  follow  the  usual  chemical  laws,  or  at  least 


250  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 

present  some  constant  relationship  which  may  be  expressed  in  an 
empirical  formula.  The  work  in  hand  has  had  for  its  object  the  pro- 
curement and  interpretation  of  data  suitable  for  the  confirmation  of 
some  such  relationship. 


METHOD  OF  ATTACK  AND  THEORY 

In  order  to  obtain  such  data  it  was  found  necessary  to  use  a  different 
method  of  attack  from  that  usually  pursued  in  a  bacteriological  problem. 
The  most  common  approach  to  such  a  problem  is  by  the  determination, 
either  in  solution  culture,  in  sand  culture,  or  in  culture  upon  the  moist 
pulverized  mineral  itself,  of  the  amount  of  material  made  soluble  by 
the  growth  of  certain  organisms.  This  method  gives  a  series  of  isolated 
results,  which,  though  no  doubt  interesting  in  themselves,  are  entirely 
unrelated  either  among  themselves  or  to  any  factor  which  may  control 
the  magnitude  of  the  bacterial  effect.  In  dealing  with  the  phase  of  the 
problem  studied  in  this  paper,  a  different  method  is  employed,  a 
method  by  which  it  is  hoped  to  show  a  certain  relationship  between  H 
ion  produced  by  bacteria  and  the  amounts  of  bases  brought  into 
solution. 

The  magnitude  of  the  effect  of  bacterial  end-products  upon  a  mineral 
will  depend  upon  the  equilibrium  involving  that  end-product  and 
mineral.  As  stated  before,  in  this  study  it  is  elected  to  deal  with  cases 
in  which  acids  are  the  end-products  in  question.  Therefore,  it  was 
deemed  necessary  first  to  study  the  equilibria  of  certain  acids,  used 
over  a  wide  range  of  concentrations,  with  certain  minerals.  The  object 
of  these  equilibrium  studies  was  to  compare  the  H  ion  concentrations 
of  the  acids,  at  the  various  molar  concentrations,  with  the  amounts  of 
material  which  are  brought  into  solution,  so  to  speak,  by  these  H  ion 
concentrations.  Later,  studies  were  made  of  the  H  ion  production  by 
certain  organisms,  and  of  the  equilibria  involving  these  acids  and  the 
minerals,  the  H  ion  and  the  amounts  of  material  in  solution  being 
determined. 

There  is  an  extensive  literature  dealing  with  the  equilibria 
of  various  soils  and  minerals  in  contact  with  solutions  of  acids,  of 
bases,  and  of  salts.  This  literature  deals  largely  with  the  absorption  of 
bases  by  soils  and  minerals,  and  with  the  exchange  of  bases  between 
solution  and  soil  or  solution  and  mineral.  In  nearly  every  instance, 
however,  the  data  are  insufficient  to  warrant  their  use  for  substitution 
in  formulae. 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  251 

The  earlier  work  is  so  ably  and  completely  reviewed  by  Sullivan,16 
in  his  consideration  of  The  Interaction  between  Minerals  and  Water 
Solutions,  that  it  seems  advisable  to  refer  the  reader  to  that  excellent 
resume  rather  than  to  attempt  a  repetition  here.  This  review  covers 
the  work  of  Thompson,17  Way,18  Eichhorn,19  Henneberg  and  Stohmann,20 
Lemberg,21  Peters,22  Liebig,23  Rautenberg,24  Van  Bemmelen,25  Armsby,26 
and  Boedeker,27  and  deals  largely  with  the  controversy  of  the  physical 
process  of  adsorption  versus  chemical  reaction  as  the  cause  of  the 
absorption  and  exchange  of  bases  in  soils. 

The  work  of  Dittrick28  is  not  included  above.  His  work  is  reported 
in  two  papers,  and  covers  experiments  with  a  granite  and  an  amphibole 
paridotite,  and  solutions  of  KC1,  NaCl,  NH4C1,  CaCl2,  MgCl2,  KN03, 
K2S04,  and  K2C03,  in  the  concentrations  N/1,  N/10,  and  N/100.  He 
found  Ca  and  Mg  dissolved  by  the  solutions,  the  least  by  N/1  solution, 
more  by  the  N/10  solution,  and  most  by  the  N/100  solution.  The 
amount  of  exchange  was  greater  with  the  more  decomposed  rock. 
Repeated  extraction  with  solutions  removed  roughly  twice  as  much 
material  as  a  single  extraction. 

The  action  of  an  acid  upon  a  silicate  is  really  an  exchange  of  H  ion 
for  any  of  the  bases  which  come  into  solution  through  its  action.  This 
exchange  is  a  reversible  chemical  reaction,  and  as  such  should  conform 
with  the  chemical  laws  applicable  to  such  reactions. 

Let  us  consider  a  simple  case  of  reversible  reaction,  or  balanced 
action,  that  of  the  union  of  hydrogen  and  iodine  to  form  hydriodic 
acid:  H2+I2-2HL 

In  this  reaction  there  is  a  point  of  equilibrium  which  is  represented 
by  the  equation : 

Ch2  X  C12  _  ki  _  „ 

Chi  K 

This  is  an  example  of  homogeneous  equilibrium,  involving  the 
gaseous  phase  only. 

A  somewhat  different  case  is  encountered  with  the  decomposition 
of  calcium  carbonate  into  carbon  dioxide  and  calcium  oxide: 

CaC03  =0=  CaO  +  C02. 

Here  we  have  both  gaseous  and  solid  phases.  The  amount  of  gas 
taking  part  in  the  reaction  may  be  measured  by  its  pressure,  but  the 
solid  must  be  considered  in  a  different  light.  This  reaction  may  be 
considered  as  taking  place  in  the  gaseous  phase,  the  solids  present  fur- 
nishing a  constant  supply  of  CaC03  and  CaO  vapor.    Then  if  C  is  the 


252  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 

pressure  of  CaC03,  Ci  the  pressure  of  CaO,  and  c  the  pressure  of  C02 
at  equilibrium,  the  equation  at  equilibrium  is: 

kC  =  kiCiC,  or  c  =  r-~r    =  K 

Going  farther  we  have  the  following  as  a  reaction  in  which  we  have 
a  solid  and  a  gas  on  both  sides  of  the  equation : 

H20  +  Fe  -  FeO  +  H2 

Let  c  be  the  concentration  of  H20,  C  that  of  Fe,  Ci  of  FeO,  and  Ci  of 
H2.   At  equilibrium  we  then  have  the  equation: 

kcC  =  ki  Ci  Ci. 

,  c       ki  Ci       T^ 
and  — =  -j— ft  =  & 
Ci       kC 

or  —  =  K 

Ci 

Now  applying  this  last  equation  to  a  case  where  we  have  a  solution 
of  a  salt  acting  upon  a  solid  to  form  another  salt  in  solution  and  a 
solid  we  will  take  the  following  reaction: 

BaS04  +  Na2C03  =c=  Na2S04  +  BaC03. 

Let  C,  c,  Ci  and  Ci  be  the  respective  concentrations  of  the  reacting 
substances.    Then  from  the  above  equation 

-=K, 

Cl 

CNa2CQ3     _    T7- 

Cn,i2&04 

This  last  equation  shows  that  the  equilibrium  point  is  measured  by  the 
ratio  of  concentrations  of  the  soluble  reacting  materials.  As  stated  by 
Walker:29  "The  active  masses  of  the  barium  salts  may  be  accounted 
constant  in  the  reaction,  for  although  they  are  generally  spoken  of  as 
'  insoluble ',  they  are  in  reality  measurably  soluble  in  water.  The  aqueous 
liquid  in  contact  with  them  will  be  and  remain  saturated  with  respect  to 
them,  i.e.,  their  concentration  and  active  mass  in  the  solution  will  be 
constant.  The  equilibrium  will  thus  be  determined  by  a  certain  ratio 
of  the  concentrations  of  the  soluble  sodium  salts,  independent  of  what 
the  actual  values  of  the  concentrations  may  be." 

A  mineral  in  contact  with  an  acid  solution  is  very  similar  to  the  last 
case  cited  above,  and  at  any  concentration  of  the  acid  the  equilibrium 
should  be  measured  by  the  ratio 

concentration  of  the  acid 


concentration  of  the  material  in  solution 
when  these  are  measured  at  equilibrium. 


=  K 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  253 

The  H  ion  is  usually  assumed  to  be  the  measure  of  the  active  acid. 
In  acid  solution  the  H  ion  concentration  is  some  function  of  the  molar 
concentration  of  the  acid.  Since  gas  chain  measurements  yield  values 
which  approach  the  theoretical  H  ion  concentration,  determinations  of 
the  H  ion  concentrations,  Ch,  by  this  method  may  be  substituted  for 
" concentration  of  acid"  in  the  above  formula  and  the  ratio 


^material  in  solution 

will  be  constant. 

When  dealing  with  materials  as  complex  in  their  chemical  structure 
as  are  minerals,  it  is  recognized  that  a  rigid  adherence  to  the  theoretical 
laws  can  not  be  expected,  and  it  becomes  necessary,  therefore,  for  a 
comprehensive  knowledge  of  such  reactions  as  are  considered  in  this 
paper,  to  resort  to  certain  empirical  formulae.  It  is  obviously  imprac- 
ticable to  attempt  to  consider  in  the  term  "  concentration  of  material 
in  solution,"  as  used  in  the  formula  above,  all  the  bases  which  may  be 
present  in  the  solution  in  contact  with  the  mineral  at  equilibrium. 
These  considerations  lead  to  the  assumption  that  any  one  of  the  bases 
may  be  taken  as  measuring  the  magnitude  of  the  action  of  the  acid  on 
the  mineral.  Consequently,  it  is  suggested  that  the  formula  thus  far 
developed  theoretically,  be  changed  to  the  empirical  formula 

— h  =  K 
Ca      ^ 

where  Ch  is  the  concentration  of  hydrogen  ion,  and  Ca  represents  the 
molar  concentration  of  Ca,  Mg,  Fe,  or  K  in  solution  at  equilibrium 
with  the  acid. 

Since  it  is  desired  to  study  the  initial  H  ion  concentration  with 
respect  to  Ca,  Mg,  Fe,  or  K  in  solution,  it  becomes  necessary  to  add  a 
still  further  modification  to  the  empirical  formula — namely,  the  expres- 
sion of  the  initial  H  ion  concentration  in  terms  of,  or  as  some  function 
of,  the  H  ion  concentration  at  equilibrium.  It  is  found  that  this  is  an 
exponential  function  of  the  H  ion  concentration  at  equilibrium.  (See 
fig.  0.) '  In  this  figure,  log.  Ch  of  the  acid  alone  is  plotted  against  log. 
Ch  of  acid  in  contact  with  the  mineral.  The  resulting  graph  is  a  straight 
line,  indicating  that  the  ratio  is  constant,  at  least  over  a  certain  range 
of  concentrations.  Thus  Ch  of  the  acid  alone  is  a  logarithmic  or  ex- 
ponential function  of  Ch  of  the  acid  in  contact  with  the  mineral,  or 

C  Cx 

Ch  =  Ch  •   Then  the  equation  —  =  K  becomes  —  =  K,  where  Ch  is  the 


254  University  of  California  Publications  in  Agricultural  Sciences        [Vol.4 

initial  H  ion  concentration  of  the  acid,  Ca  the  concentration  of  Ca,  Mg, 
Fe,  or  K  in  solution  at  equilibrium,  and  K  is  a  constant.  This  equation 
is  the  one  used  in  the  consideration  of  the  data  contained  in  this  paper. 

The  formation  of  acid  as  the  end-product  of  bacterial  activity  is  a 
property  common  to  many  organisms  including  many  which  are  com- 
monly found  in  soils.  Acid  production  by  bacteria  has  been  the  subject 
of  many  investigations.  It  is  used  as  a  means  for  identifying  the 
various  members  of  the  Colon  group  of  bacteria,  and  consequently  the 
fermentation  of  sugars  by  this  group  has  been  widely  studied.  A 
review  of  the  entire  field  will  not  be  attempted,  but  it  is  well  to  mention 
work  having  a  more  or  less  direct  bearing  upon  the  subject  in  hand. 

Harden30  studied  the  Chemical  Action  of  B.  coli  communis  and  Similar 
Organisms  on  Carbohydrates  and  Allied  Compounds.  He  found  that  the 
lactic  acid  produced  never  exceeds  one-half  of  the  sugar  fermented.  The 
amount  of  acid  formed  varies  with  the  different  sugars. 

In  a  later  study  with  Penfold  31  he  used  B.  coli  on  a  medium  com- 
posed of  2  per  cent  glucose  and  1  per  cent  peptone.  He  gets  of  alcohol, 
acetic  acid,  formic  acid,  C02,  lactic  acid,  and  succinic  acid,  respectively 
17.22  per  cent,  20.60  per  cent,  2.55  per  cent,  17.30  per  cent,  40.60  per 
cent,  and  4.80  per  cent  of  the  sugar  used.  With  a  selected  strain  of 
B.  coli,  the  lactic  acid  reaches  70  per  cent  of  the  amount  of  sugar  used. 

Michaelis  and  Marcora32  find  that  the  highest  degree  of  acidity 
produced  by  B.  coli  at  37°  C.  is  1  x  105. 

In  the  lactic  acid  fermentation  of  sugars,  Claflin33  notes  the  formation 
also  of  formic,  propionic,  and  acetic  acids,  the  acetic  acid  formation 
depending  upon  the  degree  of  aeration.  Ninety-five  to  97  per  cent  of 
the  sugar  may  be  converted  into  lactic  acid,  with  a  very  low  production 
of  volatile  acids,  not  over  one-half  per  cent.  He  claims  that  the  nature 
of  the  acid  produced  depends  upon  the  organism  and  not  upon  the 
nature  of  the  medium. 

In  the  present  work  it  must  be  shown  what  is  the  amount  of  acid,  or 
rather  the  H  ion  concentration,  produced  by  the  organisms  upon  the 
carbohydrate  media  used,  and  what  is  the  effect  of  this  concentration 
upon  the  minerals.    Is  this  effect  similar  to  that  of  the  acids  alone? 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  255 


EXPERIMENTAL  METHODS 

As  suggested  in  the  foregoing  section,  the  experimental  work  is 
divided  into  two  parts,  the  first  consisting  of  the  equilibrium  studies 
with  the  minerals  and  acid  solutions,  the  second  of  bacteriological 
studies. 

Equilibrium  studies. — The  acids  used  were  hydrochloric,  sulfuric, 
oxalic,  phosphoric,  lactic,  formic,  and  acetic.  It  will  be  observed  that 
these  acids  vary  in  the  degree  of  dissociation  for  any  given  concentra- 
tion, hydrochloric  acid  being  the  most  highly  dissociated,  and  acetic 
acid  being  the  least  ionized.  The  minerals  were  calcium  silicate,  ortho- 
clase  feldspar,  biotite,  and  granite.  They  were  ground  in  a  ball  mill  to 
pass  a  200-mesh  sieve.  The  acids  were  used  in  the  concentrations :  N/5, 
N/25,  N/50,  N/100,  N/250,  N/500,  N/1,000,  N/2,000,  N/5,000,  and 
N/10,000. 

The  work  was  carried  on  at  room  temperature.  The  equilibrium 
studies  were  arranged  in  four  series,  one  for  each  mineral,  and  each 
series  contained  a  sub-series  for  each  acid.  200  cubic  centimeters  of 
solution  were  thoroughly  shaken  with  5  grams  of  mineral,  Jena  glass- 
ware being  used.  The  solutions  were  allowed  to  remain  in  contact  with 
the  mineral  for  three  days,  which  time  is  shown  in  the  following  table 
to  be  sufficient  for  equilibrium. 

Table  Showing  the  Effect  of  the  Time  of  Contact 
upon  the  H  ion  Concentration. 

Orthoclase  +  N  5  HC1 

Days  H  ion  concentration 

1 709  xlO-1 

2 636X10-1 

3 615X10-1 

4 656  x  10-1 

5 615  x  10-1 

As  much  as  possible  of  the  supernatant  solution  was  then  pipetted 
off  and  filtered  through  a  Whatman  No.  42  filter  paper,  an  unfiltered 
portion  being  taken,  however,  for  the  H  ion  determination.  In  an 
aliquot  of  the  filtered  solution,  calcium,  iron,  magnesium,  and  potassium 
were  determined,  the  calcium  and  iron  by  titration  with  potassium 
permanganate,  the  magnesium  and  potassium  gravimetrically  as  the 
pyrophosphate  and  chloroplatinate  respectively. 


256  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 

The  H  ion  determinations  were  made  by  the  use  of  the  hydrogen 
electrode,  with  the  same  modifications  as  were  used  by  Sharp  and 
Hoagland34  for  soils.  These  determinations  are  made  both  on  the  acid 
solutions,  and  on  the  acids  in  contact  with  the  minerals. 

A  question  arose  as  to  the  possibility  of  the  formation  of  a  gelatinous 
coating  upon  the  surface  of  the  mineral,  which  would  hinder  the  further 
action  of  the  acid,  and  prevent  attainment  of  equilibrium.  In  order 
to  ascertain  whether  the  amount  of  shaking  had  been  sufficient  to 
remove  this  film  and  allow  the  reaction  to  come  to  equilibrium,  the  fol- 
lowing experiment  was  proposed.  A  5-gram  portion  of  mineral  was 
shaken  with  200  cc.  of  N/5  HC1,  as  in  the  experimental  procedure. 
The  mineral  and  solution  were  then  poured  upon  a  filter  paper,  and  the 
mineral  was  dried  and  then  ground  in  a  mortar.  H  ion  determinations 
were  made  upon  the  filtrate.  The  filtrate  was  poured  upon  the  dried 
mineral  and  allowed  to  remain  for  three  days  with  frequent  shaking. 
H  ion  determinations  were  again  made.  The  following  data  show  that 
there  is  no  significant  change  in  H  ion  concentration  in  the  second 
contact  of  the  solution  with  the  mineral : 

H  ion  Cone. 

Calcium  silicate  +N  5  HCl....lst  contact 0.607  x  10"1 

Calcium  silicate  +N  5  HC1....2d  contact..  .  .  0.607  x  10"1 

Labradorite         +N  5  HCl....lst  contact 0.797  x  10"1 

Labradorite         +N  5  HC1....2d  contact 0.828  x  10"1 

Bacteriological  work. — Three  organisms  were  used,  Azotobacter, 
Bacillus  coli,  and  B.  lactis  acidi.  The  first  of  these  was  chosen  because 
of  the  very  high  H  ion  concentration  which  it  produced  upon  dextrose 
solution,  nearly  1.  x  10_1  as  determined  by  Dr.  Waynick  in  this  labora- 
tory. B.  coli  is  referred  to  in  the  literature  previously  cited  as  producing 
large  amounts  of  acid,  and  B.  lactis  acidi  was  taken  as  a  typical  acid 
producer.  Azotobacter  were  grown  upon  2  per  cent  dextrose  solution, 
B.  coli  in  a  solution  of  2  per  cent  dextrose  and  1  per  cent  peptone  as 
used  by  Penfold,  and  B.  lactis  acidi  in  1  per  cent  dextrose.  The  work 
was  arranged  in  three  series,  one  for  each  organism.  Each  series  con- 
tained five  cultures,  each  culture  containing  1,000  cc.  of  solution  in 
1,200  cc.  Florence  flasks.  One  culture  contained  no  mineral.  The  other 
cultures  contained  25  grams  of  mineral  each,  one  with  calcium  silicate, 
one  with  orthoclase  feldspar,  another  with  biotite,  and  one  with  granite. 
These  cultures  were  run  for  a  total  time  of  sixteen  days,  H  ion  determina- 
tions  being  made  at  1,  2,  3,  5,  7,  9,  11,  and  16  days,  and  on  each  of  these 
days  100  cc.  of  solution  was  removed  for  the  determination  of  calcium, 
iron,  magnesium,  and  potassium.  The  cultures  were  grown  at  a  tem- 
perature  of  28°  C.  and  the  customary  bacteriological  precautions  were 
observed  throughout  the  work. 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  257 


DATA 

The  data  obtained  by  the  methods  given  above  are  reported  in 
tables  1  to  38  inclusive.  The  amounts  of  calcium,  magnesium,  iron,  and 
potassium  are  calculated  and  expressed  as  moles  per  liter.  Both  the 
initial  and  final  H  ion  concentrations  are  also  reported  as  gram  mole- 
cules per  liter.  For  the  convenience  of  the  reader,  the  logarithms  of 
these  numerical  values  are  given  in  adjacent  columns. 

Accompanying  each  table  is  a  graphical  representation  of  the  rela- 
tion between  certain  series  of  values  given  in  that  table.  (Owing  to  a 
loss  of  material  during  the  analysis,  tables  3,  9,  and  22  are  incomplete; 
there  are,  therefore,  no  graphs  for  these  tables.)  The  logarithms 
of  the  H  ion  concentrations,  log.  Ch,  are  plotted  along  the  ordinates, 
and  the  logarithms  of  the  concentrations  of  Ca,  Mg,  Fe,  or  k,  log.  Ca, 
along  the  abscissas,  and  the  average  curve  is  drawn  through  the  points 
thus  obtained. 

In  the  section  of  this  paper  dealing  with  "  Method  of  Attack  and 
Theory,"  certain  assumptions  are  made  and  ultimately  expressed  in  the 

Cx 

empirical  formula,  —  =  K.    By  substitution  of  the  experimental  data 

Ca 

in  this  formula,  the  values  of  the  constants  x  and  K  may  be  calculated. 
If  these  values  of  x  and  K  are  constant  for  a  given  series,  then  the  ratio, 

— ,  is  constant  for  that  series,  and  the  plotted  graph  representing  that 

Ca 

ratio  will  be  a  straight  line,  or  conversely,  a  straight  line  curve  indicates 
that  x  and  K  are  constant.  The  straight  line  graph  expresses  a  direct 
ratio  between  series  of  values,  these  values  being,  in  this  case,  the 
logarithms  of  Ch  and  of  Ca. 

The  exponential  constant  x  and  the  reasons  for  its  use  have  been 
discussed  previously.  It  expresses  the  relation  of  H  ion  at  equilibrium 
to  the  initial  H  ion  concentration  of  the  acid.  That  this  relationship  is 
of  an  exponential  character  may  be  due  to  chemical  reaction,  to  ad- 
sorption, or  to  a  combination  of  these  phenomena.  It  is  not  proposed, 
however,  to  differentiate  here  between  adsorption  and  chemical  re- 
action, the  purpose  of  this  work  being  to  provide  a  means,  empirical  if 
necessary,  of  accounting  for  the  magnitude  of  the  action  of  acids  upon 
minerals. 

The  constant  K  is  the  numerical  expression  of  the  ratio  of  the 
logarithm  of  the  initial  H  ion  concentration  to  the  logarithm  of  Ca,  Mg, 


258  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 

Fe,  of  K  brought  into  solution,  so  to  speak,  by  that  H  ion  concentration. 
The  numerical  magnitude  of  K  for  any  table  represents  the  slope  or 
inclination  of  the  graph  plotted  from  that  table.  The  range  of  values 
for  K  may  be  very  large,  varying  from  infinity,  for  a  horizontal  line, 
to  zero,  for  a  vertical  line. 

Since  it  is  possible  to  draw  a  straight  line  averaging  the  points 
plotted  from  the  experimental  data,  the  graphical  method  is  employed 
for  obtaining  values  of  log.  Ch  and  log.  Ca  for  substitution  in  the  equation 
for  the  calculation  of  x  and  K.  By  this  means  average  values  of  x  and 
K  may  be  computed  without  resorting  to  a  calculation  of  all  the  possible 
combinations  of  equations  for  which  data  are  available.  The  use  of  this 
procedure  eliminates  a  large  part  of  the  tedious  mathematical  routine, 
and  it  is  recognized  as  yielding  averages  sufficiently  close  to  the  statis- 
tical average  to  serve  the  purpose  contemplated  in  this  paper.  If  the 
above  preliminary  remarks  are  borne  carefully  in  mind,  the  following 
consideration  of  the  groups  of  tables  and  graphs  will  be  clear. 

Tables  1  to  7  contain  the  data  for  the  equilibria  between  calcium 
silicate  and  the  acids.  The  figures  accompanying  these  tables  are 
sufficient  to  show  that  the  graph  for  any  given  series  is  a  straight  line. 
As  stated  before,  this  signifies  that  x  and  K  are  constant  for  each  series, 
and  that  the  reaction  of  the  acid  with  the  mineral  takes  place  in  accord- 

ance  with  the  formula  —  =  K.    The  slope  of  the  graphs,  however,  seems 

Ca 

to  become  less  for  the  equilibria  involving  the  less  dissociated  acids,  the 
slope  for  acetic  acid  being  much  less  than  that  for  hydrochloric  acid. 
As  explained  before,  this  difference  in  slope  is  indicated  by  the 
following  numerical  values  for  the  constant  K  calculated  from  the 
graphs,  the  slope  becoming  less  as  K  increases : 

HC1 K  =  0.01391 

Sulfuric  acid K  =  0.2642 

Phosphoric  acid K  =  0.4448 

Lactic  acid K  =  14.86 

Formic  acid K  =  335.5 

Acetic  acid K  =  941.2 

Since,  as  stated  before,  the  graphs  represent  ratios  of  log.  Ch  to 
log.  Ca,  and  since  this  ratio  varies  with  the  slope  of  the  graph,  it  would 
seem,  from  a  comparison  of  the  curves  for  HC1  and  acetic  acid,  that 
an  acid  such  as  HC1,  which  is  highly  ionized,  brings  smaller  amounts  of 
materia]  into  solution  per  unit  increase  of  H  ion  than  do  those  acids, 
acetic  for  instance,  which  have  a  lower  ionization  constant.  This 
apparent  difference  in  the  action  of  various  acids  is  due  undoubtedly  to 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  259 

the  fact  that  the  commercial  calcium  silicate  was  used  for  this  work, 
and  that  it  contained  considerable  quantities  of  CaC03,  as  shown  by 
the  marked  effervescence  which  occurred  when  the  acid  was  added  to 
this  material.  The  loss  of  C02  from  the  system  undoubtedly  affected 
the  true  equilibrium,  and  this  apparently  greater  action  of  the  less 
dissociated  acids  is  the  result.  As  will  be  seen  in  the  considerations 
which  follow,  this  difference  in  effect  between  various  acids  occurs 
only  with  calcium  silicate. 

In  tables  1  to  7,  as  well  as  in  those  which  follow,  there  are  no 
data  for  calcium  where  oxalic  acid  is  used,  because  of  the  insolubility  of 
the  resulting  calcium  oxalate.  This  fact  is  mentioned  again,  and  its 
importance  is  emphasized  further,  in  connection  with  a  general  state- 
ment corcerning  the  action  of  the  H  ion  concentration  of  acids  upon 
minerals. 

The  data  for  the  various  acids  and  orthoclase  are  found  in  tables  8 
to  12  inclusive.  From  a  comparison  of  the  corresponding  graphs, 
it  is  seen  that  they  are  quite  steep,  and  that  all  have  approxi- 
mately the  same  slope.  This  observation  is  verified  by  a  consideration 
of  the  constant,  K,  as  calculated  for  the  various  members  of  this  group 
of  tables.  The  fact  that  K  is  very  small  is  evidence  that  the  graphs 
approach  the  perpendicular,  and  when  it  is  remembered  that  the  values 
for  K  range  from  zero  to  infinity  for  a  change  of  90  degrees  in  slope,  it 
is  obvious  that  the  very  small  range  of  values  for  K  given  here, 
0.00002661  to  0.000001427,  represents  a  very  small  difference  in  the 
slopes  of  the  various  curves.  The  fact  that  K  is  constant  for  each 
series,  and  that  the  corresponding  graph  is  a  straight  line,  goes  to  show 
that  the  calcium  coming  into  solution  is  a  logarithmic  function  of  the 
initial  H  ion  concentration  of  the  acid,  and  that  the  assumptions  ex- 

Cx 

pressed  in  the  formula  —  =  K  are  verified  by  experimental  evidence . 

Further  proof  of  these  assumptions  is  offered  in  the  next  group  of 
tables,  numbers  13  to  19  inclusive,  which  give  the  data  for  the  acids  in 
equilibrium  with  biotite.  Data  for  calcium,  magnesium,  and  potassium 
in  solution  are  reported.  As  in  the  previous  series  of  tables,  the  graphs 
for  calcium  are  straight  lines  and  have  about  the  same  slope,  the  extreme 
range  of  values  for  K  being  from  0.00005790  to  0.000001071.  The 
constant  K  for  the  magnesium  determinations  is  more  variable,  but 
still  no  large  discrepancy  is  apparent,  the  values  ranging  from  0.04373 
to  0.000008395. 

A  deviation  from  the  straight  line  graph  is  encountered  in  the 
figures  and  tables  expressing  the  equilibria  for  granite  and  the  acids, 


260  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 

tables  20  to  26  inclusive.  When  the  logarithms  of  the  data  for  iron  are 
plotted  against  the  logarithms  for  H  ion  concentrations  and  the  lines 
are  drawn  through  the  points  thus  obtained,  the  resulting  curves  are 
not  straight  lines.  (See  figures  20  to  26.)  The  flatter  portion  of  the 
curve  occurs  in  every  instance  at  approximately  the  value,  3.0,  repre- 
sented by  that  logarithm  of  the  H  ion  concentration,  and  probably  is 
due  to  the  formation  of  another  compound  of  iron  at  that  concentra- 
tion. Since  these  curves  are  not  straight  lines,  it  is  obvious  that  no 
constant  values  for  x  and  K  may  be  calculated  therefrom,  and  further- 
more it  may  be  inferred  that  any  iron  compounds  in  the  mineral  do  not 
react  with  the  acids  in  accordance  with  the  proposed  formula.  The 
curves  for  calcium,  however,  are  straight  lines,  thus  affording  still 
further  proof  that  the  assumptions  regarding  the  nature  of  such  re- 
actions are  correct  as  far  as  calcium  is  concerned.  The  graphs  have 
nearly  the  same  slope  throughout  the  series  of  figures,  the  values  for 
K  ranging  from  0.000001328  to  0.000007799. 

In  a  general  survey  of  the  graphs  thus  far  discussed,  instances  may 
be  observed  in  which  certain  plotted  points  are  far  from  coincident  with 
the  straight  line  graph.  In  certain  cases,  these  discrepancies  represent 
error  in  the  determinations.  Where  they  appear  in  the  lower  portion 
of  the  graph,  however,  the  last  two  -or  three  points  dropping  below  the 
curve,  they  occur  because  the  lower  limit  of  the  determination  has  been 
reached,  and  no  smaller  amounts  can  be  determined  with  any  degree 
of  accuracy. 

A  consideration  of  the  meaning  and  the  possible  relationships  of  the 
results  thus  far  reviewed  is  not  inappropriate  at  this  point.  It  is  the 
opinion  of  the  writer  that  that  type  of  investigation  is  the  most  valuable 
which  has  for  its  object  the  procurement  of  data  which  are  related, 
either  among  themselves,  or  to  certain  controllable  factors,  and  which 
may  be  taken  as  the  basis  for,  or  in  verification  of,  some  general  law 
suitable  either  for  the  explanation  of  certain  phenomena  or  for  direct 
application  in  the  prediction  of  future  results.  Thus  a  general  con- 
sideration of  the  tables  and  figures  leads  to  the  following  remarks. 

All  the  straight  line  graphs  for  a  given  mineral,  excepting  calcium 
silicate,  the  deviation  of  which  has  been  explained,  have  practically  the 
same  slope  and  give  nearly  the  same  values  for  x  and  K.  It  follows 
therefore,  that  if  the  curves  for  one  mineral  in  contact  with  the  various 
acids  be  superimposed  one  upon  the  other,  they  will  all  fall  practically 
in  the  same  straight  line.  This  would  seem  to  indicate,  for  a  given 
mineral,  and  within  the  limits  of  the  concentrations  used,  that  the  amount 
of  calcium,  magnesium,  or  potassium  coming  into  solution  is  a  function 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  261 

of  the  H  ion  concentration  of  the  acid,  regardless  of  the  nature  of  the 
acid  used,  except,  and  this  exception  is  extremely  important,  in  those 
cases  where  the  acid  forms  compounds  which  are  less  soluble  at  any 
given  H  ion  concentration  than  the  compounds  in  the  mineral  itself. 
The  importance  of  this  exception  must  be  emphasized,  and  it  is  illus- 
trated in  a  very  striking  manner  by  the  different  series  with  oxalic  acid 
where  only  traces  of  calcium  are  found  in  solution.  It  is  recognized 
that  this  illustration  represents  an  extreme  case  and  that  other  so- 
called  insoluble  compounds  may  approach  the  mineral  compounds  in 
solubility. 

The  objection  was  raised  to  the  foregoing  generalization  that  a 
N/100  solution  of  acetic  acid,  for  instance,  contains  the  same  total 
molar  concentration  of  hydrogen  as  a  N/100  hydrochloric  acid  solution, 
regardless  of  the  relative  H  ion  concentration  of  these  acids.  The  hydro- 
chloric acid  is,  of  course,  the  more  highly  dissociated  acid,  but  will  not 
the  slightly  dissociated  acetic  acid  continue  to  give  off  H  ion  as  that 
already  in  solution  combines  with  the  mineral,  and  should  not  the  ulti- 
mate result  be  the  same  with  the  acetic  as  with  the  hydrochloric  acid 
for  a  given  molar  concentration?  That  this  objection  is  not  sub- 
stantiated by  fact  is  due  doubtless  to  the  following  reason.  In  general 
the  salts  of  acetic  acid  are  much  more  highly  dissociated  than  is  the 
acid  itself.  Consequently,  the  acetates  formed  by  the  contact  of  acetic 
acid  with  the  mineral  will  be  fairly  highly  dissociated,  thus  supplying 
the  solution  at  equilibrium  with  a  certain  concentration  of  acetic  ion. 
The  presence  of  this  acetate  ion  will  depress  or  prevent  the  further 
ionization  of  the  acetic  acid  in  solution,  and  thus  practically  limit  the 
action  of  the  acetic  acid  to  its  original  H  ion  concentration.  This  same 
explanation  will  hold  for  other  slightly  dissociated  acids. 

The  general  relation  existing  between  the  H  ion  concentration  of 
acids  and  the  amounts  of  Ca,  of  Mg,  or  of  K  in  solution,  may  have  the 
following  practical  application.  It  is  desired  to  determine  the  effect  of 
certain  acids  upon  a  mineral.  This  mineral  may  be  studied  in  equi- 
librium with  different  concentrations  of  HC1,  and  the  logarithmic 
graph  constructed  as  in  the  foregoing  mineral  series.  Any  point  on  this 
graph  represents  a  ratio  of  log.  H  ion  to  log.  Ca,  or  whatever  base  it  is 
desired  to  consider,  in  solution.  Thus,  by  determining  the  H  ion  con- 
centration of  the  acid  whose  action  it  is  desired  to  predict,  we  may,  by 
referring  to  the  graph,  estimate  the  magnitude  of  the  effect  of  the  acid 
upon  the  mineral,  at  least  within  certain  limits  already  discussed.  The 
application  suggested  above  may  be  made  to  the  effect  of  acids  produced 
by  bacterial  growth,  and  in  the  prediction  of  their  action  upon  a  given 
mineral. 


262  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 

The  above  application  is  suggested  merely  as  a  possibility,  and  it  is 
fully  recognized  that  there  is  room  for  much  further  study  and  research 
before  the  existence  of  such  a  general  relationship  can  be  definitely 
established.  It  must  be  emphasized  also  that  the  constants  for  one 
mineral  and  one  set  of  conditions  can  not  be  applied  directly  to  another 
mineral  and  a  different  set  of  conditions.  The  constants  must  be  de- 
termined, and  the  resulting  graph  constructed  for  every  application  of 
the  relation  suggested. 

The  data  obtained  from  the  bacterial  series  still  await  consideration. 
As  expressed  in  tables  26  to  38,  and  in  the  corresponding  figures,  the 
action  of  the  acids  produced  by  bacteria  seems  to  differ  in  magnitude 
from  the  action  of  the  acids  used  in  the  foregoing  series.  In  regard  to 
this  difference,  it  should  be  observed  that  Ch,  the  H  ion  concentration, 
was  determined,  for  the  bacterial  series,  in  solution  cultures  with  no 
mineral  present.  Had  the  bacterial  growth  been  stopped  immediately 
following  the  H  ion  determination,  and  had  this  solution  then  been 
brought  into  contact  with  the  mineral,  the  magnitude  of  the  effect 
should  have  been  comparable  with  that  of  the  acid  series.  Instead,  the 
amounts  of  material  coming  into  solution  were  determined  in  a  series 
parallel  with  the  above,  wherein  bacteria  were  grown  in  solution  in 
contact  with  the  minerals.  It  had  been  assumed  that  the  rate  of  H  ion 
production  would  be  the  same,  both  in  solution  culture  and  in  solution 
in  contact  with  the  mineral.  This  assumption  was  found  to  be  incorrect. 
In  the  mineral  cultures  the  acid  was  partly  neutralized  as  produced, 
and  the  growth  of  the  organism  was  not  inhibited  by  the  increasing 
concentration  of  acid  as  it  was  in  the  dextrose  solution  with  no  mineral. 
Consequently,  the  total  H  ion  as  produced  in  the  mineral  cultures,  and 
indicated  by  the  large  relative  amounts  of  material  coming  into  solution 
in  these  cultures,  was  much  greater  than  that  produced  in  the  parallel 
series  without  mineral.  Since  the  data  for  H  ion,  Ch,  as  expressed  in 
the  tables,  were  obtained  from  the  latter  series,  it  is  obvious  that  the 
graphs  plotted  from  a  ratio  of  H  ion,  as  determined  in  dextrose  solution, 
to  material  in  solution,  as  determined  in  the  mineral  cultures,  are  not 
directly  comparable  with  the  graphs  for  the  equilibria  between  acids  and 
minerals. 

The  lack  of  agreement  between  the  acid  series  and  the  bacterial 
series  is  made  evident  by  a  review  of  the  curves  and  the  corresponding 
constants  for  the  bacterial  series.  The  graphs  are  straight  lines,  but 
they  have  less  slope  than  do  those  graphs  for  the  corresponding  mineral 
in  equilibrium  with  the  acids.  For  instance,  the  constant,  K,  for  ortho- 
clase  and  Azotobacter  is  19.77  against  a  value  approaching  l(h6  for 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  263 

orthoclase  and  the  acids,  and  the  graph  for  the  former  has  much 
less  slope  than  the  graph  for  the  latter.  The  constant,  K,  for  orthoclase 
and  B.  coli  is  13,490,  against  1CH5  for  orthoclase  and  the  acids.  B.  lactis 
acidi,  which  produced  acid  very  slowly,  is  represented  by  graphs  which 
more  nearly  resemble  those  of  the  acid-mineral  series,  and  the  value  for 
K  for  calcium  from  orthoclase,  for  instance,  is  0.0006652.  Since  dis- 
crepancies of  the  same  general  nature  and  magnitude  as  those  just 
pointed  out,  are  apparent  in  the  other  graphs  and  constants  for  the 
bacterial-mineral  series,  the  reader  is  referred  to  the  graphs  and  tables 
for  further  comparisons. 

The  important  point  brought  out  by  the  bacterial  series  is  that  the 
graphs  for  calcium,  for  magnesium,  and  for  potassium  are  straight  lines, 
and  that  x  and  K  are  constant  for  a  given  series.  Thus  it  is  shown  that 
the  reactions  between  minerals  and  the  acids  produced  by  bacterial 
growth,  conform  with  the  given  empirical  formula.  Since  this  same 
formula  has  been  successfully  applied  to  the  chemical  equilibria  between 
various  acid  solutions  and  the  same  minerals,  it  may  be  concluded  that 
the  action  of  bacterial  end-products  upon  minerals,  at  least  when  these 
end-products  are  acids,  is  explainable  upon  the  basis  that  it  is  a  chemical 
reaction. 

SUMMARY 

Equilibria  of  certain  minerals  and  various  concentrations  of  acids 
are  studied. 

Equilibria  of  the  same  minerals  with  solutions  in  which  bacteria  are 
producing  acid  are  also  studied. 

The  data  obtained  from  the  acid-mineral  series  are  applied  to  the 

Cx 

formula  —  =  K. 

Ca 

It  is  found  that  the  reactions  occurring  in  the  mineral-acid  equilibria 
conform  with  the  given  formula. 

It  is  suggested  that  a  general  -relation  exists  between  the  initial 
H  ion  concentration  of  the  acid  and  the  amount  of  material  which  the 
acid  brings  into  solution  when  in  contact  with  a  mineral. 

A  practical  application  of  the  relation  just  referred  to,  is  suggested. 

The  data  obtained  from  the  bacterial  studies  are  applied  to  the 

formula  —  =  K. 

Ca 

The  reactions  occurring  in  the  bacterial  series  also  conform  with  the 
above  formula. 


264  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 

It  is  concluded  that  the  action  of  acid  bacterial  end-products  upon 
minerals  is  explainable  as  a  chemical  reaction. 

The  author  wishes  to  express  his  gratitude  to  Dr.  C.  B.  Lipman 
for  the  suggestion  of  the  problem  and  for  his  interest  and  help  during 
the  progress  of  the  work,  and  to  Professor  L.  T.  Sharp  and  Dr.  D.  D. 
Way  nick  for  many  helpful  suggestions. 

Transmitted  September  2,  1919. 


LITERATURE  CITED 

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1897.  Bacteria  and  the  decomposition  of  rocks.  Am.  Jour,  of  Sci.,  vol.  153, 
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7  Lacroix,  A. 

1906.  Sur  la  transformation  de  roches  volcaniques  en  phosphate  d'alumine 
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8  Bassalik,  K. 

1913a.  Decomposition  of  silicates  by  soil  bacteria.  Zeitsch.  Garungsphysiol., 
vol.  2,  pp.  1-32. 

19136.     Silicate  decomposition  by  soil   bacteria    and    yeasts.    Ibid.,   vol.   3, 
pp.  15-42. 

9  Kawamura,  T. 

Studies  on  "Tengunomugimethi." 

10  Lipman,  J.  G.,  and  McLean,  H.  C. 

1916.  The  oxidation  of  sulphur  in  soils  as  a  means  of  increasing  the  availability 
of  mineral  phosphates.    Soil  Science,  vol.  1,  pp.  533-539. 

11  Stoklasa,  J. 

1900.  Ueber  den  Einfluss  der  Baktcrien  auf  die  Knochenzersetzung.  Central- 
blatt  fur  Bakt.,  Abt.  2,  Bd.  6,  pp.  554-560. 


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12  Koch,  A.,  and  Kroeber,  E. 

1906.  Der  Einfluss   der   Bodenbakterien  auf  das   Loslichwerden   der   Phos- 

phorsaure  aus  verschiedenen  Phosphaten.     Fiihling's  Landwirt. 
Zeit.,  vol.  55,  pp.  225-235. 

13  Kroeber,  E. 

1909.  Ueber  das  Loslichwerden  der  Phosphorsaure  aus  wasserunloslichen 
Verbindungen  unter  der  Einwerkung  von  Bakterien  und  Hefen. 
Jour,  fur  Landwirt.,  vol.  57,  pp.  5-80. 

14  Sackett,  W.  G.,  Patten,  A.  J.,  and  Brown,  C.  W. 

1908.  The  solvent  action  of  soil  bacteria  upon  the  insoluble  phosphates  of  raw 
bone  meal  and  natural  raw  rock  phosphate.  Michigan  Agric. 
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15  Hopkins,  C.  G.,  and  Whiting,  A.  L. 

1916.  Soil  bacteria  and  phosphates.  Illinois  Exper.  Station  Bull.  No.  190, 
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16  Sullivan,  E.  C. 

1907.  The  interaction  between  minerals  and  water  solutions  with  special 

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17  Thompson,  H.  S. 

1850.     On  the  absorbent  power  of  soils.  Jour.  Roy.  Agric.  Soc,  vol.  2,  pp.  68-74. 

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1852.     Idem,  Second  paper,  ibid.,  vol.  13,  pp.  123-143. 
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Agric.  Soc,  vol.  15,  pp.  491-514. 

19  Eichorn,  H. 

1858.  Ueber    die   Einwirkung   verdunnter   Salzlosungen  auf  Silicate.     Pogg. 

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20  Henneberg,  J.  W.  J.,  and  Stohmann,  F.  K.  A. 

1859.  Ueber  das  Verhalten  der  Ackererde  gegen  Losungen  von  Ammoniak  und 

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266  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 

25  Van  Bemmelen,  J.  M. 

1899.     Die  Absorption  IV.    Die  Isotherme  des  kolloidalen  Eisenoxyds  bei  15°. 

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27  BOEDEKER,  C.  VON. 

1859.  Ueber  das  Verhaltniss  zwischen  Masse  und  Wirkung  beim  Contact 
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28  DlTTRICK,  M.  VON. 

1901.  Chemisch-geologische  Untersuchungen  ueber  "Absorptionserscheinun- 
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1913.     Introduction  to  physical  chemistry.    Macmillan. 

30  Harden,  A. 

1901.  The  chemical  action  of  Bacillus  coli  communis  and  similar  organisms  on 
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31  Harden,  A.,  and  Penfold,  W.  J. 

1912.  The  chemical  action  on  glucose  of  a  variety  of  Bacillus  coli  communis 
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32  Michaelis,  L.,  and  Marcora,  F. 

1912.  Die  Saureproduktivitat  des  bacterium  coli.  Zeitschrift  Immunitats- 
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33  Claflin,  A.  A. 

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34  Sharp,  L.  T.,  and  Hoagland,  D.  R. 

1916.  Acidity  and  absorption  in  soils  as  measured  by  the  hydrogen  electrode. 
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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals 


267 


NOTE 

The  following  legend  refers  to  all  the  figures: 

+  =  Curve  for  Calcium. 

O  =  Curve  for  Magnesium. 

0  =  Curve  for  Potassium  or  Iron. 

The  numbers  along  the  ordinates  represent  the  logarithms  of  the 
H  ion  concentrations,  or  log.  Ch.  Those  along  the  abscissas  measure 
the  logarithms  of  the  concentrations,  or  log.  Ca,  of  calcium,  magnesium, 
iron,  or  potassium. 


2.0 


3.0 


4.0     _ 


5.0 


7.0  6.0  5.0  4.0  3.0  2.0 

Fig.  0. 

(See  Table  8) 

Relation  of  log.  H  ion,  HC1,  to  log.  H  ion, 

HC1  +  Orthoelase. 


268 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  I 

Hydrochloric  Acid 

and  Calcium  Silicate 

Concentration 
HC1 

Ch,  H  ion 

Hydrochloric 

Acid 

Log.  H  ion 

Hydrochloric 

Acid 

H  ion                     _     Ca,  Calcium 
Hydrochloric  Acid  Mols.  per 
+Calcium  Silicate  Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.0882 

2.94547 

0.0313 

0.00306 

3.485721 

N25 

0.0218 

2.33846 

0.00000534 

0.00218 

3.338456 

N50 

0.0135 

2.13003 

0.00000175 

0.00121 

3.02785 

N  100 

0.00685 

3.83569 

0.000000671 

0.000685 

4.835691 

N250 

0.00321 

3.50651 

0.000000131 

0.000376 

4.575188 

N500 

0.00114 

3.05690 

0.0000000842 

0.000240 

4.380211 

N  1,000 

0.000677 

4.83059 

0.0000000587 

0.000159 

4.201397 

N  2,000 

0.000281 

4.44871 

0.0000000965 

0.000122 

4.086360 

N  5,000 

0.0000326 

5.51322 

0.0000000719 

0.000120 

4.079181 

N  10,000 

0.0000192 

5.28330 

0.000000620 

0.000117 

4.068168 

Constants  for  the  equation  —  =  K : 

Ca 


x  =  0.636 
K  =  0.01391 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  269 


2.0 


3.0 


4.0 


5.0 


6.0 


5.0 


4.0 


3.0 


2.0 


Fig.  1. 

Hydrochloric  Acid  and  Calcium  Silicate. 

(See  Table  1) 


270 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  2 

Sulfuric  Acid  and  Calcium  Silicate 

Concentration 

Ch,  H  ion 

Sulfuric 

Acid 

Log.  H  ion 

Sulfuric 

Acid 

Hion 

Sulfuric  Acid 
+Calcium  Silicate 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.0567 

2.75358 

0.0300 

0.00188 

3.274158 

N25 

0.0186 

2.26951 

0.00000579 

0.00197 

3.294466 

N50 

0.0130 

2.11394 

0.000000450 

0.00115 

3.060698 

N100 

0.00632 

3.80072 

0.000000203 

0.000655 

4.816241 

N250 

0.00296 

3.47129 

0.0000000810 

0.000356 

4.551450 

N500 

0.00162 

3.20952 

0.0000000719 

0.000218 

4.338456 

N  1,000 

0.000931 

4.96895 

0.000000180 

0.000148 

4.170262 

N  2,000 

0.000600 

4.77815 

0.0000000323 

0.000099 

5.995635 

N  5,000 

0.000259 

4.41330 

0.0000000235 

0.000079 

5.897627 

N  10,000 

0.000174 

4.24055 

0.0000000364 

0.000089 

5.949390 

Constants  for  the  equation 


K: 


By  graphical  average : 
x  =  0.799 
K  =  0.2642 
By  calculation: 

x  =  0.858  ±  0.0074 
K  =  0.7332  ±  0.0313 


v.  =  5.99% 
v.  =  29.05% 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  271 


2.0 


3.0 


4.0 


5.0 


6.0 


5.0  4.0  3.0 

Figure  2. 
Sulfuric  Acid  and  Calcium  Silicate. 
(See  Table  2) 


2.0 


>72 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  3 

Oxalic  Acid  and 

Calcium  Silicate 

Concentration 

Ch,  H  ion            Log.  H  ion 
Oxalic                  Oxalic 
Acid                     Acid 

H  ion                         Ca,  Calcium 
Oxalic  Acid               Mols.  per 
+Calcium  Silicate  Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.0218             2.33846 

0.0347 

N25 

0.0110             2.04139 

0.0000192 

N50 

0.00561            3.74896 

0.00000175 

N  100 

0.00347           3.54033 

0.000000433 

N250 

0.00169           3.22789 

0.0000000941 

N500 

0.00105           3.02119 

0.0000000778 

N  1,000 

0.000554         4.74351 

0.0000000719 

N  2,000 

0.000317         4.50106 

0.0000000637 

N  5,000 

0.000132         4.12057 

0.0000000544 

N  10,000 

0.0000785       5.89487 

0.000000469 

TABLE  4 

Phosphoric  Acid 

and  Calcium  Silicate 

Concentration 

Ch,  H  ion 

Phosphoric 

Acid 

Log.  H  ion 
Phosphoric 
Acid 

H  ion                          Ca,  Calcium 
Phosphoric  Acid      Mols.  per 
+Calcium  Silicate  Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.0125 

2.09691 

0.0498 

0.00307 

3.487138 

N25 

0.00632 

3.80072 

0.00000707 

0.000872 

4.940516 

N50 

0.00424 

3.62737 

0.00000294 

0.000525 

4.720159 

N100 

0.00273 

3.43616 

0.00000054 

0.000366 

4.563418 

N250 

0.00144 

3.15836 

0.000000268 

0.000208 

4.318063 

N500 

0.000762 

4.88195 

0.0000000941 

0.000149 

4.173186 

N  1,000 

0.000372 

4.57054 

0.0000000482 

0.000109 

4.037426 

N  2,000 

0.000213 

4.32838 

0.0000000350 

0.000089 

5.949390 

N  5,000 

0.0000642 

5.80754 

0.0000000235 

0.000074 

5.869232 

N  10,000 

0.0000431 

5.63448 

0.0000000395 

0.000074 

5.869232 

Constants  for  the  equation  — —  =  K: 

Ca 


x  =  0.835 
K  =  0.4448 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  273 


2.0 


3.0 


4.0 


5.0 


6.0 


5.0  4.0  3.0  2.0 

Figure  4. 

Phosphoric  Acid  and  Calcium  Silicate. 

(See  Table  4) 


274 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  5 
Lactic  Acid  and  Calcium  Silicate 


Concentration 

N5 
N25 
N50 
N  100 
N250 
N500 
N  1,000 
N  2,000 
N  5,000 
N  10,000 


Ch,  H  ion 

Lactic 

Acid 

0.00561 

0.00252 

0.00169 

0.00114 

0.000677 

0.000472 

0.000270 

0.000189 

0.000112 

0.0000547 


Log.  H  ion 

Lactic 

Acid 

3.74896 
3.40140 
3.22789 
3.05690 
4.83059 
4.67394 
4.43136 
4.27646 
4.04922 
5.73799 


H  ion 

Lactic  Acid 
+Calcium  Silicate 

0.00577 

0.000130 

0.00000108 

0.000000572 

0.000000141 

0.0000000877 

0.0000000719 

0.0000000364 

0.0000000395 

0.000000126 


H 


Constants  for  the  equation  — - 

By  graphical  average: 
x  =  1.144 
K  =  14.86 
Constants  by  calculation 
x  =  1.118  ±  0.0368 
K  =  12.09  ±  0.326 


K: 


Ca,  Calcium 
Mols.  per 
Liter 

0.00308 

0.00201 

0.00123 

0.000812 

0.000445 

0.000208 

0.000148 

0.000099 

0.000079 

0.000074 


Log.  Calcium 
Mols.  per 
Liter 

3.488551 
3.303196 
3.089905 
4.909556 
4.648360 
4.318063 
4.170262 
5.995635 
5.897627 
5.869232 


C.  v.  =  25.9% 
C.  v.  =  12.01% 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  275 


2.0 


3.0 


4.0 


5.0 


5.0  4.0  3.0 

•    Figure  5. 
Lactic  Acid  and  Calcium  Silicate. 
(See  Table  5) 


2.0 


276 


University  of  California  Publications  in  Agricultural  Sciences        [Vol. 


TABLE  6 
Formic  Acid  and  Calcium  Silicate 


Concentration 

Ch,  H  ion 

Formic 

Acid 

Log.  H  ion 

Formic 

Acid 

H  ion 

Formic  Acid 
+Calcium  Silicate 

Ca.  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.00518 

3.71433 

0.00577 

N25 

0.00233 

3.36736 

0.0000635 

N50 

0.00156 

3.19312 

0.000000620 

0.00119 

3.075547 

N  100 

0.0010 

3.00000 

0.000000327 

0.000694 

4.841359 

N250 

0.000762 

4.88195 

0.0000000719 

0.000365 

4.563481 

N500 

0.000472 

4.67394 

0.0000000522 

0.000208 

4.318063 

N  1,000 

0.000343 

4.53529 

0.0000000350 

0.000138 

4.139879 

N  2,000 

0.000181 

4.25768 

0.0000000276 

0.000119 

4.075547 

N  5,000 

0.0000753 

5.87679 

0.0000000245 

0.000099 

5.995635 

N  10,000 

0.0000398 

5.59988 

0.0000000719 

0.0000248 

5.394452 

Constants  for  the  equation 


C 


K: 


x  =  1.324 
K  =  335.5 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals 


277 


2.0 


3.0 


4.0 


5.0 


5.0  4.0  3.0 

Figure  6. 
Formic  Acid  and  Calcium  Silicate. 
(See  Table  6) 


2.0 


278 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  7 

Acetic  Acid  and 

Calcium  Silicate 

Concentration 

Ch,  H  ion 

Acetic 

Acid 

Log.  H  ion 

Acetic 

Acid 

H  ion 

Acetic  Acid 
+Calcium  Silicate 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.00224 

3.35025 

0.000547 

0.00285 

3.454845 

N25 

0.000860 

4.93450 

0.00000797 

0.00250 

3.397940 

N50 

0.000677 

4.83059 

0.00000100 

0.00126 

3.100371 

N  100 

0.000454 

4.65706 

0.000000279 

0.000742 

4.870404 

N250 

0.000387 

4.58771 

0.000000116 

0.000347 

4.540329 

N500 

0.000213 

4.32838 

0.0000000350 

0.000178 

4.250420 

N  1,000 

0.000189 

4.27646 

0.0000000395 

0.0000892 

5.950365 

N  2,000 

0.000104 

4.01703 

0.0000000350 

0.0000694 

5.841359 

N  5,000 

0.0000884 

5.94645 

0.000000116 

0.0000694 

5.841359 

N  10,000 

0.0000414 

5.61700 

0.000000238 

0.0000495 

5.694605 

Constants  for  the  equation 

Ca 

x  = 

1.465 

K  = 

941.2 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  279 


2.0 


3.0 


4.0 


5.0 


5.0  4.0  3.0 

Figure  7. 

Acetic  Acid  and  Calcium  Silicate. 

(See  Table  7) 


2.0 


280 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  8 

Hydrochloric  Acid  and  Orthoclase 

Concentration 

Ch,  H  ion 

Hydrochloric 

Acid 

Log.  H  ion 

Hydrochloric 

Acid 

H  ion 

Hydrochloric  Acid 
+Orthoclase 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.0882 

2.94547 

0.0615 

0.00159 

3.201397 

N25 

0.0218 

2.33846 

0.0218 

0.001449 

3.159567 

N50 

0  0135 

2.13003 

0.00836 

0.001045 

3.019116 

N100 

0.00685 

3.83569 

0.00296 

0.00094 

4.973128 

N250 

0.00321 

3.50651 

0.000554 

0.000685 

4.835691 

N500 

0.00114 

3.05690 

0.0000784 

0.000565 

4.752048 

N  1,000 

0.000677 

4.83059 

0.000000935 

0.00056 

4.748188 

N  2,000    . 

0.000281 

4.44871 

0.00000110 

0.00040 

4.602060 

N  5,000 

0.0000326 

5.51322 

0.000000261 

0.00038 

4.579784 

N  10,000 

0.00000192     6.28330 
Constants  for  Calcium: 

0.00000010 

0.000336 

4.526339 

x  = 

0.225 

K  = 

0.000006310 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids -and  Minerals  281 


2.0 


3.0 


4.0 


5.0 


6.0 


5.0  4.0  3.0  2.0 

Figure  8. 
Hydrochloric  Acid  and  Orthoclase. 
(See  Table  8) 


282  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  9 

Oxalic  Acid 

AND    ORTHOCLASE 

Concentration 

Ch,  H  ion 

Oxalic 

Acid 

Log.  H  ion 

Oxalic 

Acid 

H  ion 

Oxalic  Acid 
+Orthoclase 

Ca,  Calcium 
Mols.  per 
Liter. 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.0218 

2.33846 

0.0245 

N25 

0.0110 

2.04139 

0.00905 

N50 

0.00561 

3.74896 

0.00376 

N100 

0.00347 

3.54033 

0.000650 

N250 

0.00169 

3.22789 

0.00000564 

N500 

0.00105 

3.02119 

0.000000735 

N  1,000 

0.000554 

4.74351 

0.000000438 

N  2,000 

0.000317 

4.56937 

0.000000294 

N  5,000 

0.000132 

4.12057 

0.00000294 

N  10,000 

0.0000785 

5.89487 

0.00000294 

TABLE  10 

Lactic  Acid 

AND   ORTHOCLASE 

Concentration 

Ch,  H  ion 

Lactic 

Acid 

Log.  H  ion 

Lactic 

Acid 

H  ion 

Lactic  Acid 
+Orthoclase 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.00561 

3.74896 

0.00441 

0.001190 

3.075547 

N25 

0.00252 

3.40140 

0.00123 

0.00094 

4.973128 

N50 

0.00169 

3.22789 

0.000650 

0.00077 

4.886491 

N100 

0.00114 

3.05690 

0.000372 

0.000495 

4.694605 

N250 

0.000677 

4.83059 

0.000181 

0.00073 

4.863323 

N500 

0.000472 

4.67394 

0.0000414 

0.000495 

4.694605 

N  1,000 

0.000270 

4.43136 

0.00000322 

0.000465 

4.667453 

N  2,000 

0.000189 

4.27646 

0.00000217 

0.000475 

4.676694 

N  5,000 

0.000110 

4.04139 

0.000000282 

0.000366 

4.563481 

N  10,000 

0.0000547 

5.73799 

0.000000261 

0.000238 

4.376577 

Constants  for  Calcium : 

x  = 

0.324 

K  = 

0.00002661 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  283 


2.0 


3.0 


4.0 


5.0 


5.0 


4.0  3.0 

Figure  10. 
Lactic  Acid  and  Orthoclase. 
(See  Table  10) 


2.0 


284 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  11 

Formic  Acid 

AND    ORTHOCLASE 

Concentrator 

Ch,  H  ion 
Formic 
l         Acid 

Log.  H  ion 

Formic 

Acid 

Hion 

Formic  Acid 
+Orthoclase 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.00518 

3.71433 

0.00296 

0.000862 

4.935507 

N25 

0.00233 

3.36736 

0.000677 

0.000812 

4.909556 

N50 

0.00156 

3.19312 

0.000270 

0.000723 

4.859138 

N100 

0.0010 

3.00000 

0.0000957 

0.000713 

4.853090 

N250 

0.000762 

4.88195 

0.0000153 

0.000605 

4.781755 

N500 

0.000472 

4.67394 

0.00000579 

0.000535 

4.728354 

N  1,000 

0.000343 

4.53529 

0.000000197 

0.000535 

4.728354 

N  2,000 

0.000181 

4.25768 

0.000000197 

0.000495 

4.694605 

N  5,000 

0  0000753 

5.87679 

0.000000205 

0.000475 

4.676694 

N  10,000 

0.0000398 

5.59988 

0.0000000923 

0.000426 

4.629410 

Constants  for  Calcium: 

x  = 

0.142 

K  = 

0.000001427 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  28i. 


2.0 


3.0 


4.0 


5.0 


5.0 


4.0  3.0 

Figure  11. 
Formic  Acid  and  Orthoclase. 
(See  Table  11) 


2.0 


286 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  12 

Acetic  Acid 

AND   ORTHOCLASE. 

Concentration 

Ch,  H  ion 

Acetic 

Acid 

Log.  H  ion 

Acetic 

Acid 

H  ion 

Acetic  Acid 
+Orthoclase 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

N5 

0.00224 

3.35025 

0.000472 

0.000074 

4.869232 

N25 

0.000860 

4.93450 

0.000132 

0.000058 

4.763428 

N50 

0.000677 

4.83059 

0.0000696 

0.00062 

4.792392 

N100 

0.000454 

4.65706 

0.0000431 

0.00065 

4.812913 

N250 

0.000387 

4.58771 

0.0000179 

0.00051 

4.707570 

N500 

0.000213 

4.32838 

0.00000745 

0.00048 

4.681241 

N  1,000 

0.000189 

4.27646 

0.00000225 

0.00043 

4.633468 

N  2,000 

0.000104 

4  01703 

0.000000627 

0.00039 

4.591065 

N  5,000 

0.0000884 

5.94645 

0.000000438 

0.00033 

4.518514 

N  10,000 

0.0000414 

5.61700 

0.000000261 

0.00029 

4.462398 

Constants  for  Calcium : 

x  = 

0.235 

K  = 

0.000006966 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  287 


2.0 


3.0 


4.0 


5.0 


5.0 


4.0  3.0 

Figure  12. 
Acetic  Acid  and  Orthoclase. 
(See  Table  12) 


2.0 


288  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  289 


2.0 


3.0 


4.0 


5.0 


6.1 


I  ll         +1 


5.0  4.0  3.0 

Figure  13. 
Hydrochloric  Acid  and  Biotite. 
(See  Table  13) 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  295 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  297 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  303 


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Hydrochloric  Acid  and  Granite. 

(See  Table  20) 


2.0 


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University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  305 


2.0 


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Figure  21. 
Sulfuric  Acid  and  Granite. 
(See  Table  21) 


2.0 


306 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.4 


TABLE  22 
Oxalic  Acid  and  Granite 


Concentration 

Ch,  H  ion 

Oxalic 

Acid 

Log.  H  ion 

Oxalic 

Acid 

N5 

0.0213 

2.33846 

N25 

0.0110 

2.04139 

N50 

0.00561 

3.74896 

N  100 

0.00347 

3.54033 

N250 

0.00169 

3.22789 

N500 

0.00105 

3.02119 

N  1,000 

0.000554 

4.74351 

N  2,000 

0.000317" 

4.50106 

N  5,000 

0.000132 

4.12057 

N  10,000 

0.0000785 

5.89487 

H  ion 

Oxalic  Acid 
+Granite 


Ca,  Iron 
Mols.  per 
Liter 


Log.  Iron 
Mols.  per 
Liter 


0.0255 

0.00772 

0.00226 

0.00000129 

0.0000141 

0.00000254 

0.000000863 

0.000000421 

0.000000241 

0.000000261 


TABLE  23 

Phosphoric  Acid  and  Granite 

Concen- 
tration 

Ch,  H  ion 

Phosphoric 

Acid 

Log.  H  ion 
Phosphoric 
Acid 

H  ion 

Phosphoric  Acid 
+Granite 

Ca,  Iron 
Mols.  per 
Liter 

Log.  Iron 
Mols.  per 
Liter 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calci- 
um Mols. 
per  Liter 

N5    . 

0.0125 

2.09691 

0.001 

0.00496 

3.695482 

0.00174 

3.232996 

N25 

0.00632 

3.80072 

0.00296 

0.00410 

3.612784 

0.000119 

4.075547 

N50 

0.00424 

3.62737 

0.0001 

0.00351 

3.545307 

0.000178 

4.250420 

N  100 

0.00273 

3.43616 

0.0000486 

0.00716 

3.334454 

0.000515 

4.711807 

N250 

0.00144 

3.15836 

0.00000461 

0.000675 

4.829304 

0.000505 

4.703291 

N500 

0.000762 

4.88195 

0.000000232 

0.000308 

4.488551 

0.000416 

4.619093 

N  1,000 

0.000372 

4.57054 

0.000000117 

0.000188 

4.274158 

0.000436 

4.639486 

N  2,000 

0.000213 

4.32838 

0.0000000787 

0.000159 

4.201397 

0.000386 

4.586587 

N  5,000 

0.0000642 

5.80754 

0.0000000961 

0.000148 

4.170262 

0.000297 

4.472756 

N  10,000  0.0000431 

5.63448 

0.000000222 

0.000119 

4.075547 

0.000376 

4.575188 

Constants  for  Calcium: 

x  =  0.136 

K  =  0.000001987 

• 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  307 


!.0 


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Figure  23. 
Phosphoric  Acid  and  Granite. 
(See  Table  23) 


2.0 


308  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  309 


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Figure  24. 

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310 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  311 


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2.0 


312 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  313 


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Acetic  Acid  and  Granite. 

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2.0 


314 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  27. 

Obthoclase  and 

AZOTOBACTER. 

Time 
Days 

Ch,  H  ion 
Dextrose 
+Azotobacter 

Log.  H  ion 

Dextrose 

+Azotobacter 

H  ion 

Orthoclase 

+Azotobacter 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

0 

0.00000282 

6.450249 

0.000000962 

0.000238 

4.376577 

1 

0.00000261 

6.416641 

0.000000787 

0.000675 

4.829304 

2 

0.00000331 

6.519828 

0.00000161 

0.000455 

4.658011 

3 

0.00000359 

6.555094 

0.000000887 

0.000575 

4.774517 

5 

0.00000421 

6.624282 

0.000000887 

0.000852 

4.930440 

7 

0.00000534 

6.727541 

0.00000197 

0.00107 

3.029384 

9 

0.00000627 

6.797268 

0.00000251 

0.00404 

3.606381 

11 

0.00000935 

6.970812 

0.00000331 

0.00198 

3.296665 

16 

0.0000177 

5.247973 

0.00000389 

0.00119 

3.075547 

Constants  for  Calcium : 

x  = 

1.804 

K  = 

19.77 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  315 


4.0 


5.0 


6.3 


4.0 


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Figure  27. 

Orthoclase  and  Azotobacter. 

(See  Table  27) 


316 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  317 


4.0       _ 


5.0 


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4.0 


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Figure  28. 
Biotite  and  Azotobacter. 
(See  Table  28) 


318  University  of  California  Publications  in  Agricultural  Sciences        [Vol.4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  319 


4.0 


5.0 


6.3 


4.0 


3.0 
Figure  29. 
Granite  and  Azotobacter. 
(See  Table  29) 


320 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  30 

Calcium  Silicate 

AND   AZOTOBACTER 

Time 
Days 

Ch,  H  ion 
Dextrose 

+Azotobacter 

Log.  H  ion 

Dextrose 

+Azotobacter 

H  ion 

Calcium  Silicate 

+Azotobacter 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
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Liter 

0 

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6.450249 

0.0000000778 

0.00142 

3.152288 

1 

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6.416641 

0.0000000778 

0.00201 

3.303196 

2 

0.00000331 

6.519828 

0.0000000912 

0.00186 

3.269513 

3 

0.00000359 

6.555094 

0.0000000912 

0.00196 

3.292256 

5 

0.00000421 

6.624282 

0.0000000112 

0.00279 

3.445604 

7 

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6.727541 

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9 

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6.797268 

0.000000107 

0.00396 

3.597695 

11 

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6.960812 

0.0000000778 

0.00396 

3.597695 

16 

0.0000177 

5.247973 

0.000000731 

0.00406 

3.695482 

Constants  for  Calcium: 

x  = 

1,280 

K  = 

0.03381 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals 


321 


4.0 


5.0 


6.3 


4.0  3.0 

Figure  30. 
Calcium  Silicate  and  Azotobacter. 
(See  Table  30) 


322 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  31 

Orthoclase 

and  B.  Coli 

Time 

Days 

Ch,  H  ion 
Dextrose 
+B.  Coli 

Log.  H  ion 
Dextrose 
+B.  Coli 

H  ion 

Orthoclase 
+B.  Coli 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

0 

0.00000261 

6.416641 

0.000000962 

0.000694 

4.841359 

1 

0.000301 

4.478566 

0.000141 

0.000753 

4.876795 

2 

0.000486 

4.686636 

0.000267 

0.00206 

3.313867 

3 

0.000505 

4.703291 

0.000339 

0.00230  . 

3.361728 

5 

0.000505 

4.703291 

0.000289 

0.00224 

3.350248 

7 

0.000467 

4.669317 

0.000278 

0.00270 

3.431364 

9 

0.000414 

4.617000 

0.000237 

11 

0.000467 

4.669317 

0.000313 

0.00282 

3.450249 

16 

0.000431 

4.634477 

0.000179 

0.00271 

3.432969 

Constants  for  Calcium: 

x  = 

1.690 

K  = 

13,490.0 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  323 


4.0 


5.0 


4.0 


3.0 
Figure  31. 
Orthoclase  and  B.  Coli. 
(See  Table  31) 


324  University  of  California  Publications  in  Agricultural  Sciences        [Vol.4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  325 


4.0 


5.0 


4.0 


3.0 
Figure  32. 
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(See  Table  32) 


326  University  of  California  Publications  in  Agricultural  Sciences        [Vol.4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  327 


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4.0 


3.0 
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(See  Table  33) 


328 


University  of  California  Publications  in  Agricultural  Sciences        [Vol. 


TABLE  34 

Calcium  Silicate 

and  B.  Coli 

Time 
Days 

Ch,  H  ion 
Dextrose 
+B.  coli 

Log.  H  ion 
Dextrose 
+B.  coli 

H  ion 

Calcium  Silicate 

+B.  coli 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calm 
Mols.  per 
Liter 

0 

0.000000261        6.416614 

0.000000220 

0.00337 

3.527630 

1 

0.000301 

4.478566 

0.0000716 

0.0108 

2.033424 

2 

0.000486 

4.686636 

0.0000564 

0.0397 

2.598791 

3 

0.000505 

4.703291 

0.0000687 

0.0526 

2.720986 

5 

0.000535 

4.728354 

0.0000806 

0.0723 

2.859138 

7 

0.000567 

4.753583 

0.0000745 

0.0848 

2.928396 

9 

0.000584 

4.766413 

0.0000716 

0.0972 

2.987666 

11 

0.000597 

4.775974 

0.0000716 

0.1018 

T.007748 

16 

0.000579 

4.762679 

0.0000635 

0.1238 

1.092721 

Constants  for  Calcium: 
x  =  5.070 
K  =  1,667.  X  1011 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  329 


4.0 


5.0 


3.5 


2.0 

Figure  34. 

Calcium  Silicate  and  B.  coli. 

(See  Table  34) 


1.0 


330 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


TABLE  35 

Orthoclase  and 

B.  Lactis  Acidi 

Time 
Days 

Ch,  H  ion                  Log.  H  ion 

Dextrose                    Dextrose 

+B.  lactis  acidi        +B.  lactis  acidi 

H  ion 
Orthoclase 
+B.  lactis  acidi 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

0 

0.00000421 

6.624282 

0.000000354 

0.00147 

3.167317 

1 

0.0000157 

5.195900 

0.00000935 

0.000912 

4.959995 

2 

0.000228 

4.357935 

0.00000967 

0.000852 

4.930440 

3 

0.000398 

4.599883 

0.00000967 

0.00162 

3.209515 

5 

0.000642 

4.807535 

0.0000217 

0.00228 

3.357935 

7 

0.000696 

4.842609 

0.0000170 

0.00235 

3.371068 

9 

0.000696 

4.842609 

0.0000192 

0.00249 

3.396199 

11 

0.000789 

4.897077 

0.0000244 

0.00271 

3.432969 

16 

0.000642 

4.807535 

0.0000286 

0.00210 

3.322219 

Constants  for  Calcium : 

x  = 

0.867 

K  = 

0.0006652 

1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  331 


4.0 


5.0 


4.0  3.0 

Figure  35. 

Orthoclase  and  B.  lactis  acidi. 

(See  Table  35) 


332  University  of  California  Publications  in  Agricultural  Sciences        [Vol.4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  333 


3.0 
Figure  36. 
Biotite  and  B.  lactis  acidi. 
(See  Table  36) 


334  University  of  California  Publications  in  Agricultural  Sciences        [Vol.  4 


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1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  335 


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Granite  and  B.  lactis  acidi. 
(See  Table  37) 


336 


University  of  California  Publications  in  Agricultural  Sciences        [Vol.4 


TABLE  38 

Calcium  Silicate  and  B.  Lactis  Acidi 

Time 
Days 

Ch,  H  ion 
Dextrose 
+B.  lactis  acidi 

Log.  H  ion 

Dextrose 

+B.  lactis  acidi 

H  ion 

Calcium  Silicate 

+B.  lactis  acidi 

Ca,  Calcium 
Mols.  per 
Liter 

Log.  Calcium 
Mols.  per 
Liter 

0 

0.00000421 

6.624282 

0.0000000877 

0.00229 

3.359835 

1 

0.0000157 

5.195900 

0.000000136 

0.00248 

3.394452 

2 

0.000228 

4.357935 

0.000000142 

0.00475 

3.676694 

3 

0.000398 

4.599883 

0.0000000778 

0.00416 

3.619093 

5 

0.000642 

4.807535 

0.0000000778 

0.00486 

3.686636 

7 

0.000696 

4.842609 

0.0000000411 

0.00554 

3.743510 

9 

0.000696 

4.842609 

0.0000000544 

0.00545 

3.736397 

11 

0.000789 

4.897077 

0.0000000544 

0.00525 

3.720159 

16 

0.000642 

4.807535 

0.0000000544 

0.00565 

3.752048 

Constants  for  Calcium : 
x  =  0.170 
K  =  0.0000002710 


1922]         Wright:  Equilibrium  Studies  With  Certain  Acids  and  Minerals  337 


4.0 


5.0 


4.0  3.0 

Figure  38. 
Calcium  Silicate  and  B.  lactis  acidi. 
(See  Table  38) 


